JP2013222623A - 非水電解質二次電池 - Google Patents
非水電解質二次電池 Download PDFInfo
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- JP2013222623A JP2013222623A JP2012094086A JP2012094086A JP2013222623A JP 2013222623 A JP2013222623 A JP 2013222623A JP 2012094086 A JP2012094086 A JP 2012094086A JP 2012094086 A JP2012094086 A JP 2012094086A JP 2013222623 A JP2013222623 A JP 2013222623A
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- positive electrode
- layer
- porosity
- secondary battery
- porous layer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
【解決手段】本発明により、電池ケースの内圧が上昇することによって作動する電流遮断機構を備える非水電解質二次電池が提供される。この非水電解質二次電池は、前記非水電解質二次電池に含まれる非水電解質がガス発生剤を含有し、前記非水電解質二次電池を構成する正極と負極の間には、異なる多孔度を有する少なくとも2つの多孔質層が配置されており、前記少なくとも2つの多孔質層のうち、前記正極に対向する位置に配置される多孔質層Aの多孔度は、前記負極側に配置される多孔質層Bの多孔度より大きい。
【選択図】図3
Description
Li(LiaNixCoyMnz)O2
(前式中のa、x、y、zはa+x+y+z=1を満足する実数)で表される三元系リチウム遷移金属複合酸化物が挙げられる。
[正極シートの作製]
正極活物質としてLi[Ni1/3Co1/3Mn1/3]O2粉末と、導電材としてアセチレンブラック(AB)と、結着材としてポリフッ化ビニリデン(PVDF)とを、これらの材料の質量比が91:6:3となるようにN−メチル−2−ピロリドン(NMP)で混合して、ペースト状の正極合材層形成用組成物を調製した。この組成物を、長尺シート状のアルミニウム箔(正極集電体:厚さ15μm)の両面に合計塗付量が30mg/cm2(固形分基準)となるように均一に塗付し、乾燥後、圧縮することによってシート状の正極(正極シート)を作製した。正極合材層の密度は2.8g/cm3であった。正極合材層の多孔度は35%であった。
負極活物質として天然黒鉛粉末と、結着材としてスチレン−ブタジエン共重合体(SBR)と、増粘材としてカルボキシメチルセルロース(CMC)とを、これらの材料の質量比が98:1:1となるようにイオン交換水で混合して、ペースト状の負極合材層形成用組成物を調製した。この組成物を、長尺シート状の銅箔(厚さ14μm)に塗付量が17mg/cm2(固形分基準)となるように均一に塗付し、乾燥後、圧縮することによって、シート状の負極(負極シート)を作製した。負極合材層の密度は1.4g/cm3であった。
フィラー層を形成する基材として、ポリプロピレン/ポリエチレン/ポリプロピレンからなる三層構造の長尺シート状セパレータ(厚さ:20μm、多孔度:40%)を用意した。フィラー層は以下のようにして形成した。フィラーとしてアルミナと、結着材としてアクリル系バインダと、増粘材としてCMCとを、これらの質量比が96.7:2.6:0.7となるようにイオン交換水で混合することによってペースト状の組成物を調製した。混合は、エム・テクニック(株)製の超音波分散機「クレアミックス」を用いて、予備分散を15000rpmで5分行い、本分散を20000rpmで15分行った。得られた組成物をセパレータの片面に塗付し、70℃で乾燥させた。このようにして、片面にフィラー層が形成されたセパレータを得た。フィラー層の厚さは5μmであり、多孔度は55%であった。
上記のようにして作製した正極シートと負極シートとを、それぞれ3.5cm角となり、かつタブを有するように切断し、タブ部の合材層を剥がしとって、シール付きリードを取り付けた。正極シート1枚に対し、2枚の負極シートを重ね合わせた。正極シートと負極シートの間に上記フィラー層付きセパレータを挟み込んで電極体を作製した。このとき、セパレータのフィラー層が正極シートに対向するように配置した。この電極体をアルミラミネートフィルム製の袋に収容し、非水電解液を袋内に注入した。非水電解液としては、エチレンカーボネート(EC)とジメチルカーボネート(DMC)とエチルメチルカーボネート(EMC)との3:4:3(体積比)混合溶媒に、支持塩として約1mol/LのLiPF6を溶解し、さらにシクロヘキシルベンゼン(CHB)1%とビフェニル(BP)1%を含有させた電解液を用いた。袋内を真空にひきながらアルミラミネートフィルムとリードに取り付けられたシール部とを熱溶着した。さらに2枚のSUS(Steel Use Stainless)の拘束板とクリップを用いて挟み込み、合材層部分を拘束した状態のラミネート型リチウムイオン二次電池を作製した。
フィラー層の多孔度、セパレータの多孔度、正極合材層の多孔度を表1に示すように異ならせた他は例1と同様にしてラミネート型リチウムイオン二次電池を作製した。
作製した各リチウムイオン二次電池に対し、25℃の環境下にて1Cレートで4.1Vまで充電し、4.1Vになった時点で電流が0.1Cになるまで定電圧(CV)充電を行った。そして1Cで3Vまで放電した。この充放電を3回繰り返した後、次に述べる過充電試験を行った。まずSOC(State of Charge)100%でSUSの拘束板を外し、水で満たしたビーカーに水没させ、その体積(A0)を測定した。このとき、電池がビーカーに触れないようにピンセットで調整した。電池をビーカーから取り出し、再度SUSの拘束板で挟み込んだ後、25℃の環境下と60℃の環境下で、それぞれ1CレートでSOCが140%になるまで過充電を行った。なお、SOC100%とは、1Cレートで4.1Vまで充電し、4.1Vになった時点で電流が0.1CになるまでCV充電を行った状態とし、SOC0%は1Cで3Vまで放電した状態と定義した。SOC140%でSUSの拘束板を外し、水を満たしたビーカーに水没させ、この体積(A1)を測定した。このとき、上記と同様、電池がビーカーに触れないようにピンセットで調整した。上記で得たA1−A0をガス発生量(体積)とし、これを電池容量で除すことで、過充電時のガス発生量(cc/Ah)(mL/Ah)を求めた。結果を表1に示す。
10 正極シート(正極)
12 正極集電体
14 正極合材層
20 負極シート(負極)
22 負極集電体
24 負極合材層
25 非水電解液
30 CID
32 変形金属板
33 湾曲部分
34 接続金属板
35 集電リード端子
36 接合点
38 絶縁ケース
40,40A,40B セパレータ
41 樹脂層
41A,41B,41C 樹脂層
42 フィラー層
43 フィラー層
50 電池ケース
52 ケース本体
54 蓋体
70 正極端子
72 負極端子
74 正極集電板
76 負極集電板
100 リチウムイオン二次電池
Claims (7)
- 電池ケースの内圧が上昇することによって作動する電流遮断機構を備える非水電解質二次電池であって、
前記非水電解質二次電池に含まれる非水電解質がガス発生剤を含有し、
前記非水電解質二次電池を構成する正極と負極の間には、少なくとも2つの多孔質層が配置されており、
前記少なくとも2つの多孔質層のうち、前記正極に対向する位置に配置される多孔質層Aの多孔度は、前記負極側に配置される多孔質層Bの多孔度より大きい、非水電解質二次電池。 - 前記少なくとも2つの多孔質層は、前記多孔質層Aおよび前記多孔質層Bから構成されている、請求項1に記載の非水電解質二次電池。
- 前記多孔質層Aの多孔度は55%以上であり、前記多孔質層Bの多孔度は50%以下である、請求項1または2に記載の非水電解質二次電池。
- 前記多孔質層Aおよび前記多孔質層Bの一方は樹脂層であり、他方はフィラー層である、請求項1から3のいずれかに記載の非水電解質二次電池。
- 前記多孔質層Aおよび前記多孔質層Bがともに樹脂層である、請求項1から3のいずれかに記載の非水電解質二次電池。
- 前記多孔質層Aの多孔度は、前記正極を構成する正極合材層の多孔度より大きい、請求項1から5のいずれかに記載の非水電解質二次電池。
- 請求項1から6のいずれかに記載の非水電解質二次電池を備える車両。
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JP2017174647A (ja) * | 2016-03-24 | 2017-09-28 | 株式会社豊田中央研究所 | 電極構造体及びリチウム二次電池 |
JP2020102318A (ja) * | 2018-12-20 | 2020-07-02 | Tdk株式会社 | 二次電池用セパレータ層、電極構造体および二次電池 |
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JP2011065849A (ja) * | 2009-09-17 | 2011-03-31 | Hitachi Maxell Ltd | 電池用セパレータおよびリチウム二次電池 |
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JP2011065849A (ja) * | 2009-09-17 | 2011-03-31 | Hitachi Maxell Ltd | 電池用セパレータおよびリチウム二次電池 |
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WO2016111185A1 (ja) * | 2015-01-05 | 2016-07-14 | Necエナジーデバイス株式会社 | 電極およびそれを用いたリチウムイオン二次電池 |
JPWO2016111185A1 (ja) * | 2015-01-05 | 2017-11-02 | Necエナジーデバイス株式会社 | 電極およびそれを用いたリチウムイオン二次電池 |
JP2017174647A (ja) * | 2016-03-24 | 2017-09-28 | 株式会社豊田中央研究所 | 電極構造体及びリチウム二次電池 |
JP2020102318A (ja) * | 2018-12-20 | 2020-07-02 | Tdk株式会社 | 二次電池用セパレータ層、電極構造体および二次電池 |
JP7159848B2 (ja) | 2018-12-20 | 2022-10-25 | Tdk株式会社 | 二次電池 |
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